4014 Langmuir 2002, 18, 4014-4019

Surface Functionalization and Stabilization of Mesoporous

Silica Spheres by Silanization and Their Adsorption
Characteristics
Akihiko Matsumoto,*,† Kazuo Tsutsumi,† Kai Schumacher,‡ and Klaus K. Unger‡
Department of Materials Science, Toyohashi University of Technology, Tempaku-cho,
Toyohashi 441-8580, Japan, and Institut für Anorganische Chemie und Analytische Chemie,
Johannes Gutenberg Universität, Duesbergweg 10-14, D-55128 Mainz, Germany

Received January 2, 2002. In Final Form: March 5, 2002

Siliceous MCM-48 spheres are tailored with silane coupling agents, n-octyldimethylchlorosilane (C8)
and (3-aminopropyl)triethoxysilane (APTS). The changes in adsorption features of water and acetaldehyde
with the modifications are elucidated by aid of adsorption calorimetry. The MCM-48 surface exhibits a
hydrophobic feature after the C8 treatment, and the hydrophobicity is retained by repetition of water
sorption, although the surface of crude MCM-48 easily changes to hydrophilic by water adsorption. The
APTS treatment drastically increases an adsorptivity of acetaldehyde vapor. The adsorbed amount of
acetaldehyde is saturated at ca. 5 mmol/g for crude MCM-48; however, that for the APTS-treated sample
is three times higher at equilibrium pressure (Pe) of ca. 6 kPa and monotonically increases at Pe > 6 kPa.
Differential heats of adsorption during the mesopore filling of acetaldehyde are 53-70 kJ/mol, which is
much higher than the heat of liquefaction (27.2 kJ/mol) of acetaldehyde, suggesting that chemical reactions
of adsorbed acetaldehyde take place on the surface.

Introduction chemically tailored by covalently anchoring functional

Mesoporous silica materials with regular pore struc-
tures, such as MCM-41 and MCM-48,1,2 have lately
attracted considerable attention because of their ap-
plicability as model mesoporous materials in adsorption
study,3 packing materials in selective separation,4,5 ca-
talysis,6 and reaction space for structural directing
synthesis of organic and inorganic materials.7 Mesoporous
silica, MCM-48, has a regular cubic pore structure indexed
in the space group Ia3d.8 These pores are branched and
interwoven with each other; therefore, they provide more
favorable mass transfer kinetics than those of MCM-41
with unidimensional pore arrays.8,9 The mesoporous
structure of MCM-48 gives rise to a high surface area of
up to 1100 m2/g and a specific pore volume of up to 0.8
mL/g.9
Porous silica materials have been applied to adsorbents
for selective adsorption and separation processes.10,11 The
internal surface of the porous silica materials has been
* To whom correspondence should be addressed. TEL: +81-532-
44-6811. FAX: +81-532-48-5833. E-mail: aki@tutms.tut.ac.jp.
† Toyohashi University of Technology.
‡ Johannes Gutenberg Universität.
(1) Beck, J. S.; Vartuli, J. C.; Roth, W. J.; Leonowicz, M. E.; Kragse,
C. T.; Schmitt, K. D.; Chu, C. T.-W.; Olson, D. H.; Sheppard, E. W.;
McCullen, S. B.; Higgins, J. B.; Schlenker, J. L. J. Am. Chem. Soc. 1992,
114, 10834.
(2) Kregse, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck,
J. S. Nature 1992, 359, 710.
(3) Schumacher, K.; Ravikovitch, P. I.; Du Chense, A.; Neimark, A.
V.; Unger, K. K. Langmuir 2000, 16, 4648.
(4) Grün, M.; Kurganov, A. A.; Schacht, S.; Schüth, F.: Unger, K. K.
J. Chromatogr., A 1996, 740, 1.
(5) Thoelen, C.; Van de Walle, K.; Vankelecom, F. J.; Jacobs P. A.
Chem. Commun. 1999, 2177.
(6) For example: Corma, A. Chem. Rev. 1997, 97, 2373.
(7) For example: Brunel, D.; Sutra, P.; Fajula, F. Stud. Surf. Sci.
Catal. 2000, 129, 773 and references therein.
(8) Monnier, A.; Schüth, F.; Huo, Q.; Kummer, D.; Margolese, D.;
Maxwell, R. S.; Stuckey, G. D.; Krishnamurty, M.; Petroff, P.; Firouzi,
A.; Janikce, M.; Chmelka, B. F. Science 1993, 261, 1299.
(9) Schumacher, K.: Grün, M.; Unger, K. K. Microporous Mesoporous
Mater. 1999, 27, 201.
groups to impart a high selective adsorptivity and a
reactivity toward distinct target molecules,10,12 and the
tailoring technique has been also applied to the meso-
porous materials.13
This paper reports an attempt to control the surface
nature of the MCM-48 surface by silanization with silane
coupling agents providing specific surface features. The
first attempt is hydrophobic control of the MCM-48 surface
by n-octyldimethylchlorosilane, which brings about the
hydrophobic nature and improves the stability against
hydrolysis of siloxane on the MCM-48 surface. Although
the surface of freshly prepared mesoporous silica mainly
consists of siloxane so that it has hydrophobic character,
the surface siloxane easily hydrolyzes to silanol by water
adsorption and the surface becomes hydrophilic.14,15
Therefore, stabilization of the hydrophobic nature is
important to utilize the silica material for adsorption in
the presence of water vapor. Second, the modification of
MCM-48 by (3-aminopropyl)triethoxysilane was at-
tempted. The modification would confer chemisorptivity
for other chemicals such as acetaldehyde, which is one of
the odor components, allowing it to be removed from the
indoor atmosphere. The characterization of the surface
nature of the silanized silica materials and the adsorption
characteristics for water and acetaldehyde were also
elucidated with the aid of adsorption calorimetry.
(10) Unger, K. K. In Packings and Stationary Phases in Chromato-
graphic Techniques Catalysis; Unger, K. K., Ed.; Dekker: New York,
1990; Chapter 6.
(11) Unger, K. K. Porous Silica; Elsevier: Amsterdam, 1979.
(12) Vansant, E. F.; van der Voort, P.; Vrancken, K. C. Characteriza-
tion and Chemical Modification of the Silica Surface; Elsevier: Am-
sterdam, 1995; Chapter 5.
(13) For example: Van Der Voort, P.; Vansant, E. F. Stud. Surf. Sci.
Catal. 2000, 129, 317. Moller, K.; Bein, T Chem. Mater. 1998, 10, 2950.
(14) Matsumoto, A.; Sasaki, T.; Nishimiya, N.; Tsutsumi, K. Langmuir
2001, 17, 47.
(15) Matsumoto, A.; Sasaki T.; Nishimiya, N.; Tsutsumi, K. Colloids
Surf., A 2002, 203, 185.

10.1021/la020004c CCC: $22.00 © 2002 American Chemical Society

Published on Web 04/17/2002
Functionalization of Mesoporous Silica Spheres Langmuir, Vol. 18, No. 10, 2002 4015

Experimental Section
Preparation of Spherical MCM-48. Spherical particles of
mesoporous silica, MCM-48, were prepared by hydrolysis of
tetraethoxysilane similar to the procedure reported in a previous
paper.9 n-Hexadecyltrimethylammonium bromide (19.2 g, 98%,
Aldrich) was dissolved in deionized water (800 mL), and then
ethanol (400 mL, analytical grade, denatured with ca. 1% methyl
ethyl ketone, Merck) was added to the surfactant solution. Then
ammonia solution (90 mL, extra pure, 32%, Merck) was dissolved
in the surfactant solution as a catalyst and stirred vigorously for
10 min. Tetraethoxysilane (32 g, TEOS, TES28SQ, Wacker) was
added while stirring at 298 K. After the mixture was stirred for
20 h, the resulting suspension was filtered out, washed with 1
L of deionized water to remove excess surfactant on the filtrate,
and dried in air at 363 K. The sample was heated to 823 K at
a rate of 1 K/min, kept at this temperature for 5 h, and then
cooled to room temperature. This calcination process burnt out
all carbon species originating from the surfactant.
Surface Tailoring by Silane Coupling Agents. n-Octyl-
dimethylchlorosilane treatment (C8 modification). The MCM-48
(5 g) was dried for 24 h at 423 K in vacuo in order to remove
physisorbed water and placed to cool to room temperature under
a nitrogen flow. Dry dichloromethane (140 mL, 99.7%+, Sigma-
Aldrich) was added to the MCM-48. Then, 1-methyl-2-pyrroli-
dinone (1.8 g, Merck-Schuchardt) and n-octyldimethylchloro-
silane (3.6 g, 97% +, ABCR) were added to the suspension under
stirring. The suspension was put onto reflux while stirring at
333 K for 4 h under nitrogen atmosphere. The tailored silica was
then suction filtered and thoroughly washed three times with
50-mL portions of dichloromethane followed by one time with 50
mL of diethyl ether. The tailored sample was designated as MCM-
48-C8.
(3-Aminopropyl)trimethoxysilane Treatment (APTS
Modification).16 The MCM-48 (8 g) was dried for 24 h at 423
K in vacuo and placed under a nitrogen flow. The solution in
which 5.2 g of (3-aminopropyl)triethoxysilane (97%, ABCR)
dissolved in 115 mL of toluene (anhydrous, 99.8%, Aldrich) was
added to the MCM-48 at room temperature. The suspension was
kept stirring for 4 h at 298 K. The treated silica was suction
filtered, washed three times with 50-mL portions of toluene, and
heated at 423 K for 4 h. The modified sample was designated as
MCM-48-NH2.
Physicochemical Characterization. X-ray diffraction (XRD)
patterns were measured on an automatic powder diffractometer
(Seifert TT3000) using Cu KR radiation. The nitrogen adsorption
isotherms were measured volumetrically at 77 K using an
automatic adsorption apparatus (Quantachrome Autosorb 6B).
The samples were outgassed at 423 K and 1 mPa for 12 h before
the adsorption measurements. The carbon content was deter-
mined by elemental analysis (Yanaco CHN corder NT-6). The
densities of n-octyl and 3-aminopropyl ligands were calculated
from the carbon content of the tailored mesoporous silicas using
the specific surface area. Particle morphology was observed by
a scanning electron microscope (SEM, Zeiss DSM962). Fourier
transform infrared (FT-IR) spectra were measured by the KBr
method using an FT-IR spectrometer (JASCO FT/IR-420). Solid-
state 29Si MAS NMR spectra were measured on a spectrometer
(Varian VNMR400P) equipped with a magic angle spinning
(MAS) probe.
Water and Acetaldehyde Adsorption. Differential heats Figure 1. Scanning electron microphotographs of MCM-48
of adsorption of water and acetaldehyde were measured at 298 (a), MCM-48-C8 (b), and MCM-48-NH2 (c). Inset bar scale in
K with a twin conduction type microcalorimeter (Tokyo Riko) each photograph corresponds to 2 µm.
equipped with a volumetric adsorption apparatus. Each adsorp-
tion isotherm was consecutively measured with calorimetric Results and Discussion
measurements. Sample was preevacuated at 1 mPa and 423 K
for 12 h before each measurement. In regard to water adsorption, Characterization of Samples. Figure 1 shows the
the adsorption isotherms and differential heats with and without scanning electron microscopy (SEM) photographs of MCM-
the repetition of water adsorption were measured as follows to 48 before/after the surface modifications. MCM-48 par-
confirm the hydrophobic/hydrophilic change of the surface. First, ticles were spherical with particle diameters ranging from
the adsorption isotherms and differential heats of adsorption
0.3 to 0.7 µm as shown in Figure 1a. Spherical morphology
were measured until ca. 0.8 Pa. After the first adsorption run
was finished, the sample was evacuated at the same condition of the particle was retained after the silanization treat-
as the first run and the second measurement was carried out. ments. These results show that the silanization treatments
do not affect the particle morphology. The XRD pattern
(16) Kelly, D. J.; Leyden, D. E. J. Colloid Interface Sci. 1991, 147, of MCM-48 shown in Figure 2 exhibited clear peaks at 2θ
213. ) 2.67°, 3.06°, 4.52°, and 5.10° assigned to the reflections
4016 Langmuir, Vol. 18, No. 10, 2002
Table 1. Characteristics of MCM-48 and Silanized Samples
specific
surfac median pore
sample area/m2 g-1 diameter/nm
MCM-48 1200 2.4
MCM-48-C8 1190 1.6
MCM-48-NH2 710 1.8
Figure 2. X-ray diffraction patterns of MCM-48, silanized
MCM-48.
Figure 3. Adsorption isotherms of nitrogen on MCM-48 and
silanized MCM-48: circle, MCM-48; triangle, MCM-48-C8;
square, MCM-48-NH2.
from (211), (220), (421), and (332) planes of a cubic pore
structure indexed in the space group Ia3d, suggesting the
formation of MCM-48.1,8 The unit cell parameter (a) was
8.1 nm estimated from the 211 reflection. In the case of
MCM-48-C8 and -NH2, the diffraction peaks assigned to
cubic structure were observed while the peaks became
broader. These results suggest that the regular pore
structure was retained after the silanization treatments.
As shown in Figure 3, the nitrogen adsorption isotherm
of MCM-48 was of type IV with a step due to capillary
condensation at the relative pressure (P/P0) between 0.21
and 0.35.17 The average pore diameter determined by the
BJH method was 2.4 nm. On the other hand, the clear
step was not observed in the case of MCM-48-C8 and
-NH2. However, the pore size analysis by the BJH method
revealed a presence of pores of uniform diameter of 1.6-
1.8 nm, as shown in Table 1. Considering the XRD results,
it is suggested that the mesopore of MCM-48 is narrowed
by anchoring of n-octyldimethyl or 3-aminopropyl groups
with the C8 or APTM treatments. As shown in Table 1,
the modified samples still have mesopores with high
surface areas and pore volumes, which are applicable to
adsorption experiments.
(17) Rouquerol, F.; Rouquerol, J.; Sing, K. Adsorption by Powders
and Porous Solids; Academic Press: London, 1999; Chapter 1.
Matsumoto et al.
mesopore ligand density
volume/mL g-1 groups nm-2 mmol g-1
1.1
1.0 0.8 1.7
0.6 0.8 1.7
Figure 4. 29Si NMR spectra of MCM-48, MCM-48-C8, and
MCM-48-NH2.
The ligand densities of the tailored functional groups
on MCM-48-C8 and MCM-48-NH2 were determined by
elemental analysis and were 0.8 groups/nm2 or 1.7 mmol/g
for both n-octyldimethylsilyl and 3-aminopropyl groups
(Table 1).
29
Si NMR spectrum of the MCM-48 exhibited two
resonance signals at -110 and -100 ppm, as shown in
Figure 4a. The main intense signal at -110 ppm can be
assigned to Q4 units corresponding to four siloxane
bridges.18,19 The shoulder peak at -100 ppm is assigned
to Q3 units corresponding to silicon with three siloxane
bridges and one silanol. After the C8 modification, the
intensity of the shoulder signal at -100 ppm decreased
relative to the main intense signal and the new signal
assigned to silicone with two methyl and one alkyl groups
appeared at 14 ppm (Figure 4b).20,21 These spectral changes
indicate that surface silanol groups react with n-octyl-
dimethylchlorosilane and the n-octyldimethylsilyl groups
are anchored on the surface. In the case of the APTM
modification as shown in Figure 4c, several signals
attributable to the silicon atom attaching aminopropyl
group were observed at -49 ppm (unidentate anchored,
-Si(C3H6NH2)(OR)2, R:H or C2H5), -59 ppm (bidentate,
>Si(C3H6NH2)(OR)-), and -67 ppm (tridentate, tSi-
C3H6NH2), respectively, besides the Q3 and Q4 signals at
-100 and -110 ppm, respectively.20,22 These results
suggest that the surface of MCM-48 is successfully
modified also by the APTM treatment.
Water Sorption. The water adsorption isotherms on
MCM-48 and MCM-48-C8 are shown in Figure 5. The
water adsorption isotherm on MCM-48 for the first
adsorption run was of type V, suggesting a weak adsor-
(18) For example: Maciel, G. E.; Ellis, P. D In NMR Techniques in
Catalysis; Bell, A. T., Pines, A., Eds.; Dekker: New York, 1994; Chapter
5.
(19) Van Blaaderen, A.; Vrij, A. In The Colloid Chemistry of Silica;
Advances in Chemistry Series 234; Bergna, H. E., Ed.; American
Chemical Society: Washington, DC, 1994; Chapter 4.
(20) Maciel, G. E.; Bronnimann, C. E.; Ziegler, R. C.; Chuang, I.-S.;
Kinney, D. R.; Keiter, E. A. In The Colloid Chemistry of Silica; Advances
in Chemistry Series 234; Bergna, H. E., Ed.; American Chemical
Society: Washington, DC, 1994; Chapter 4.
(21) Bayer, E.; Albert, K.; Reiners, J.; Nieder, M.; Müller, D. J.
Chromatogr. 1983, 264, 197
(22) De Haan, J. W.; Van Den Bogaert, H. M.; Ponjeé, J. J.; Van De
Ven, L. J. M. J. Colloid Interface Sci. 1986, 110, 591.
Functionalization of Mesoporous Silica Spheres
Figure 5. Adsorption isotherms of water on MCM-48 and
MCM-41-C8. Circular and triangle symbols stand for MCM-48
and MCM-48-C8, respectively. Open and closed symbols denote
the first and the second adsorption runs, respectively.
Figure 6. Differential heats of adsorption of water on MCM-
48 and MCM-41-C8. Circular and triangle symbols stand for
MCM-48 and MCM-48-C8, respectively. Open and closed
symbols denote the first and the second adsorption runs,
respectively.
bate-adsorbent interaction. The adsorptivity was low at
P/P0 < 0.4, and an adsorbed amount steeply increased at
0.42 < P/P0 < 0.59 due to capillary condensation. However,
the type of isotherm changed to type IV in the second run,
which indicates a stronger interaction between the surface
and water molecules. The adsorbed amount increased to
two to three times that of the first run in the lower P/P0
region. The condensation step shifted to a lower P/P0 value
(P/P0 ) 0.3) due to decrease of an effective pore diameter
by multilayer adsorption of water molecules. These results
suggest the surface of MCM-48 changes hydrophilic
characterization during the first adsorption run. Since
such phenomena are also observed in the case of another
mesoporous silica, FSM16, we consider the water adsorp-
tion mechanism in the present case would be similar to
that of FSM16.14,15 Namely, the hydrophobic surface of
MCM-48 mainly consists of siloxane bridges and fewer
silanol groups, and the surface siloxane bridges are
hydrolyzed by adsorbed water to form silanols in the first
adsorption run to bring about higher adsorptivity in the
second run.
As shown in Figure 6, the changes in differential heats
of adsorption of water also indicated the hydrophobic-
hydrophilic change with water adsorption. In the first
adsorption run, the differential heat of adsorption was ca.
80 kJ/mol at an initial stage of the adsorption, and then
the differential heats immediately decreased as the
adsorption proceeded, attaining a constant value of ca. 45
kJ/mol at the adsorbed amount of 0.98 mmol/g. However,
in the second adsorption run, the high heat evolution
decreased rather gradually from 80 to 45 kJ/mol as the
adsorption proceeded until the adsorbed amount reached
3.2 mmol/g. Since the high heat evolution is due to strong
hydrophilic interaction between water molecules and
Langmuir, Vol. 18, No. 10, 2002 4017
Figure 7. Adsorption isotherms of acetaldehyde on MCM-48
and silanized MCM-48: circle, MCM-48; triangle, MCM-48-
C8; square, MCM-48-NH2. Whole Pe range (a) and Pe less than
10 kPa (b) are shown.
silanols,14,15 the changes in the heat curves between the
first and second runs also indicate that the MCM-48
surface becomes hydrophilic by the first adsorption run.
On the other hand, the water adsorption isotherm of
MCM-48-C8 was of Henry type;17 the adsorption amount
increased linearly with increasing P/P0, as shown in Figure
5. The water adsorptivity of MCM-48-C8 was lower than
that of MCM-48 through the whole P/P0 range, and the
adsorption isotherm in the first run was in accord with
that of the second adsorption runs. Moreover, the step
increase of uptake due to capillary condensation was not
observed. The n-octyldimethylsilyl group exhibits hydro-
phobicity because of its nonpolar character. As shown in
Table 1, the ligand density of the n-octyldimethylsilyl
group is 0.8 groups/nm2. Since a surface area covered with
one n-octyldimethylsilyl group is ca. 0.7 nm2 by considering
the molecular structure,23 the n-octyldimethylsilyl groups
would well cover most of the surface of MCM-48-C8. Thus,
the surface siloxane was protected from hydrolysis by
water adsorption. The differential heats of adsorption of
water for MCM-48-C8 ranged from 30 to 40 kJ/mol in
both the first and the second adsorption runs as shown
in Figure 6, which were lower than those for MCM-48.
These results also indicate the hydrophobic nature of
MCM-48-C8.
Acetaldehyde Adsorption. Figure 7a shows the
adsorption isotherms of acetaldehyde at 298 K. The
isotherm of MCM-48 was of type IV, with clear “knee” or
point B was observed at equilibrium pressure (Pe) of 4.6
kPa.17 The isotherm has a step at the Pe range between
36 and 50 kPa. The Kelvin pore diameters giving rise to
the step at the Pe range were estimated as 1.6-2.2 nm
with assuming the surface tension, the molar volume and
the saturated vapor pressure of acetaldehyde at 298 K as
20.5 N/m, 57.14 mL/mol, and 120.1 kPa, respectively.23,24
The Kelvin pore diameters reasonably coincided with that
estimated by the nitrogen adsorption as shown in Table
4018 Langmuir, Vol. 18, No. 10, 2002
Figure 8. Differential heats of adsorption of water on MCM-
48 and MCM-41-NH2: circle, MCM-48; triangle, MCM-48-C8;
square, MCM-48-NH2.
1. Therefore, the step at 36 kPa < Pe < 50 kPa is due to
capillary condensation of acetaldehyde vapor in the
mesopores.
Figure 8 shows the differential heats of adsorption of
acetaldehyde on MCM-48. The differential heat of ad-
sorption was 49 kJ/mol at the initial stage of adsorption,
and then it decreased monotonically as the adsorption
proceeds, attaining a constant value of ca. 30 kJ/mol. Initial
higher heat would be due to a polar interaction between
surface silanol and aldehyde groups. Afterward, the
adsorbed acetaldehyde in the mesopore behaved as liquid
phase since the adsorption heats were similar to the heats
of liquefaction of acetaldehyde, 27.2 kJ/mol. The adsorbed
amount when adsorption heats reached constant were
found to be equal to that at the beginning of the
condensation step in the isotherm shown in Figure 7a.
These results suggest that acetaldehyde molecules interact
with the surface at the initial stage and condense as a
liquid phase in the mesopores by capillary condensation.
The adsorptivity on MCM-48-C8 was the lowest among
all of samples, as shown in Figure 7a, since polar
acetaldehyde molecules weakly interact with the nonpolar
surface of the C8-modified sample. Although the dif-
ferential heat of adsorption shown in Figure 8 was 48
kJ/mol at the initial stage of the adsorption, it immediately
decreased to 25-28 kJ/mol with progress of adsorption.
The lower heat evolution also shows the weak interaction
between the acetaldehyde molecule and the MCM-48-C8
surface.
On the other hand, the adsorptivity on MCM-48-NH2
markedly increased especially Pe < 10 kPa as shown in
Figure 7a. The adsorption isotherm at 0 < Pe < 10 kPa
was magnified and is shown in Figure 7b. The adsorption
isotherm on MCM-48-NH2 exhibited type IV character
until Pe ) 6.4 kPa; however, the adsorption uptake
increased continuously over the Pe range. A careful
analysis revealed that the adsorption isotherm has
inflection points at Pe ) 0.88, 2.38, and 6.23 kPa. The
adsorption uptake at the first inflection point (Pe ) 0.88
kPa) was comparable to the amount of 3-aminopropyl
ligands, 1.7 mmol/g. Considering the high heat evolution
in this region, which will be discussed later, acetaldehyde
molecules strongly interact with the 3-aminopropyl groups
on the surface at Pe < 0.88 kPa.
The adsorbed amount increased abruptly in 0.88 kPa
< Pe < 2.38 kPa. The adsorption uptake at Pe ) 2.38 kPa
is 8.4 mmol/g or 0.53 mL/g with assuming the tentative
(23) The Chemical Society of Japan, In Kagaku Binran (Data books
of Chemistry); Maruzen: Tokyo, 1984; Chapter 8. Reid, R. C.; Prausnitz,
J. M.; Sherwood, T. K. The Properties of Gases and Liquids, 3rd ed.;
McGraw-Hill: NewYork, 1977.
(24) Jira, R.; Laib, R. J. In Ullman’s Encyclopedia of Industrial
Chemistry, 5th completely revised ed.; VCH Velagsgesellschaft: Wein-
heim, 1985; Vol. A1, pp 33-44.
Matsumoto et al.
density of adsorbed acetaldehyde is the same as that of
the liquid phase, 0.78 g/mL. This adsorbed volume
reasonably coincides with the mesopore volume deter-
mined by the nitrogen adsorption, 0.6 mL/g. Therefore,
the adsorption in the region of 0.88 < Pe < 2.38 kPa would
be condensation in the mesopores. The condensed acet-
aldehyde molecules would react with one another judging
from the heat evolution in this adsorption region, which
will be discussed later. The adsorbed amount gently
increased at 2.38 kPa due to completion of the mesopore
filling, and then it began to increase steeply at Pe > 6.2
kPa. Acetaldehyde molecules would not condense on an
external surface at Pe > 6.2 kPa since the saturated vapor
pressure at 298 K, 120 kPa, is still higher than Pe.
Therefore, the increase in the adsorbed amount at Pe >
6.2 kPa would be due to multilayer adsorption or dis-
solution in adsorbed acetaldehyde species on the external
surface. The differential heats of adsorption in this region
also indicated that the adsorption is physisorption rather
than chemisorption.
The differential heats of adsorption of acetaldehyde for
MCM-48-NH2 showed a different tendency from those for
MCM-48 and MCM-48-C8, as shown in Figure 8. The
adsorption heat was 70 kJ/mol at the initial stage of
adsorption and was retained at 53-64 kJ/mol until the
adsorbed amount attained 7.5 mmol/g. These heats were
higher than those on MCM-48 and MCM-48-C8, suggest-
ing a stronger interaction between the surface of MCM-
48-NH2 and adsorbed acetaldehyde molecules. The ad-
sorbed amount that brought about the initial higher heats
of 70 kJ/mol was 1.2-1.7 mmol/g, which corresponded to
the amount of 3-aminopropyl ligands as already men-
tioned. Therefore, the initial heats would be due to
chemisorption of acetaldehyde molecules on 3-aminopropyl
groups. The following high heats of 64-53 kJ/mol were
retained until the adsorption amount attained to 8.9 mmol/
g, which well corresponds to the adsorption amount of
mesopore filling, 8.4 mmol/g as already discussed. Such
a high heat evolution in mesopore filling suggests that
acetaldehyde molecules would not merely condense but
react in the mesopores. The plausible reaction pathway
will be mentioned later based upon IR results. The
differential heats then decreased to 30-39 kJ/mol. Since
the evolved heats were similar to the heat of liquefaction
of acetaldehyde at 239 K, acetaldehyde may condense and/
or dissolve in preadsorbed acetaldehyde. Thus, the silani-
zation with 3-aminopropyl groups is possible to impart
chemical activity on the surface.
Figure 9 shows IR spectra of samples before and after
acetaldehyde adsorption. The spectrum of MCM-48 before
acetaldehyde adsorption exhibited bands assigned to silica
and adsorbed water at 3440 cm-1 (the O-H stretching of
adsorbed water and the hydrogen bonded silanol groups),
1640 cm-1 (the O-H bending of adsorbed water), 1250-
1000 cm-1 (the Si-O asymmetrical stretching of siloxane),
970 cm-1 (the Si-O-(H...H2O) bending), and 800 cm-1
(in-plane bending of geminal silanol).25 After acetaldehyde
adsorption, a new band appeared at 1720 cm-1 which was
assigned to the CdO stretching vibration of crude ac-
etaldehyde.26 This result shows that acetaldehyde is
physisorbed on MCM-48 as predicted by the measurement
of the differential heats of adsorption.
The IR spectrum of MCM-48-C8 exhibited absorption
bands assigned to the C-H stretching vibration of methyl
(25) Vansant, E. F.; van der Voort, P.; Vrancken, K. C. Stud. Surf.
Sci. Catal. 1995, 93, 59.
(26) Silverstein, R. M.; Bassler, G. C.; Morril, T. C. Spectroscopic
Identification of Organic Compounds, 5th ed.; Wiley: New York, 1981;
Chapter 3.
Functionalization of Mesoporous Silica Spheres
Figure 9. IR spectral changes for MCM-48 and silanized MCM-
48 with acetaldehyde adsorption: a, before adsorption; b, after
adsorption.
and methylene groups at 2962 cm-1 (asymmetrical
stretching, CH3), 2930 cm-1 (asymmetrical stretching,
CH2), and 2860 cm-1 (symmetrical stretching, CH3),
besides the absorption bands due to silanol groups and
siloxane. It should be noted that the absorbance of the
absorption bands due to the O-H vibrations of silanol
and adsorbed water decreased, suggesting the hydropho-
bicity of the surface of MCM-48-C8. Since the adsorbed
amount of acetaldehyde on MCM-48-C8 was much smaller
than MCM-48, apparent changes in IR spectra were not
detected by acetaldehyde adsorption.
The IR spectrum of MCM-48-NH2 exhibited weak bands
assigned to the C-H stretching vibration of methyl and
methylene groups in the anchored ligands at 2970-3000
cm-1, as shown in Figure 8.26 Upon acetaldehyde adsorp-
tion, the bands assigned to adsorbed acetaldehyde ap-
peared at 2970-3000 cm-1. The bands assigned to the
C-H symmetrical bending vibrations of methylene and
methyl groups also appeared at 1455 and 1378 cm-1,
respectively.26 Besides these bands, a new band appeared
at 1678 cm-1, which was attributable to the stretching
vibrations of CdO in R,β-unsaturated aldehydes.26 The
CdO vibration of acetaldehyde gives strong bands at 1730
cm-1;27 however, the band was not observed in the
spectrum of MCM-48-NH2 after acetaldehyde adsorption.
These results suggest that acetaldehyde molecules are
chemisorbed in pores of MCM-48-NH2 giving rise to R,β-
(27) Pouchert, C. J. The Aldrich Library of FT-IR Spectra, Edition
I; Aldrich Chemical Co. Inc.: New York, 1985; Vol. 1, p 465A.
Langmuir, Vol. 18, No. 10, 2002 4019
unsaturated aldehydes. Since the primary amino group
of 2-aminopropyl ligand exhibits basicity, it may interact
with R-hydrogen of an acetaldehyde molecule to form an
enolate anion (CH2CHO-). The enolate ion reacts with
another acetaldehyde molecule by aldol condensation to
give rise to 2-butenal (crotonaldehyde, CH3CdCHCHO).27
The condensation products would also react with other
aldehydes by cross aldol condensation and may give rise
to R,β-unsaturated aldehydes. The continuous evolution
of higher heats until the adsorbed amount of 8.9 mmol/g,
shown in Figure 8, supports that the aldol condensation
reaction would take place in mesopores. Thus, the chemi-
cally active MCM-48-NH2 surface chemisorbs acetalde-
hyde molecules and exhibits high adsorptivity.
Conclusions
The surface properties of MCM-48 spheres are suc-
cessfully controlled by silanization. The silanization by
n-octyldimethylchlorosilane imparts hydrophobicity and
stability against hydrolysis by water adsorption although
the surface of crude MCM-48 changes to hydrophilic by
hydrolysis of siloxane bridges to silanol with water
adsorption. The surface of MCM-48 is chemically inert
and does not have a particular adsorptivity for acetal-
dehyde. However, the adsorptivity of acetaldehyde is
drastically enhanced with silanization by (3-aminopropyl)-
triethoxysilane. The acetaldehyde adsorption on MCM-
48-NH2 is chemisorption with high heat evolution. Judging
from the differential heat of adsorption and IR spectral
changes with the adsorption, acetaldehyde molecules react
by the aldol condensation mechanism. Thus, the possibility
to control the surface nature of MCM-48 is shown in this
study. Especially, the spherical MCM-48-NH2 has such a
high chemical activity with high surface area and pore
volumes. Therefore, it would be applicable to an efficient
mesoporous adsorbate for aldehydes, which would be
applicable as a deodorizer of cigarette smoke and as column
packing materials for chromatographic separation. The
application of such silanized mesoporous silica spheres
will be further studied.
Acknowledgment. The authors are indebted to Dr.
Yukihiro Motoyama and Professor Hisao Nishiyama,
Toyohashi University of Technology, for their kind help
and suggestions on elemental analysis and discussion of
IR and NMR results. A.M. thanks Deutsche Akademischer
Augstauschdienst (German Academic Exchange Service)
for partial financial support of his research stay in
Germany. The financial support by a Grant-in-Aid for
Science Research, Japan Society for the Promotion of
Science, and a Project Research Grant, Toyohashi Uni-
versity of Technology, are greatly appreciated.
LA020004C